JP5047896B2 - Novel bistrimellitic anhydride esters and polyesterimide precursors obtained from it and diamines - Google Patents

Description

  The present invention relates to novel bistrimellitic anhydride esters and polyesterimide precursors obtained from bistrimellitic anhydrides and diamines, and more specifically, mainly 1,1-bis (4-oxyphenyl) -3,3,5-trimethylcyclohexane. The present invention relates to a bis trimellitic anhydride ester as a skeleton and a polyesterimide precursor obtained by reacting such a bis trimellitic anhydride ester with a diamine.

Bis-trimellitic anhydride esters have been used as epoxy resins, polyurethane resin curing agents, polyesterimide resin raw materials, and the like. As such bis trimellitic anhydride esters, for example, bis trimellitic anhydride ester compound of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) (Patent Document 1), '-Methylene bisphenol (bisphenol F), 4,4'-(1,3-dimethylbutylidene) bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4 '-(1 -Phenylethylidene) bisphenol, bistrimellitic anhydride ester compounds such as 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane (Patent Document 2) ), 4,4′-biphenol, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 ′ [1,3-phenylene bis (1-methylethylidene)] bis trimellitic anhydride ester compound of bisphenol (Patent Document 3) are known.
Moreover, about the polyesterimide precursor, 2,2-bis (4-hydroxyphenyl) tridecane, 1,1-bis (4-hydroxyphenyl) cyclohexane anhydride trimellitic acid ester compound and a polyesterimide precursor from diamine ( Patent Document 4) is known.

  However, in recent years, particularly, polyesterimide resins have been used for various applications, and depending on the applications, further performance improvements such as heat resistance have been demanded. Therefore, as a result of intensive studies on the trimellitic anhydride ester compound as a raw material, the present inventors have found 1,1-bis (4) in which three methyl groups are substituted at specific positions of the cyclohexane ring of the central skeleton, which is a novel ester compound. -Oxyphenyl) -3,3,5-trimethylcyclohexane bis-trimellitic anhydride ester, and polyester imide precursors obtained from it and diamines meet the demands for improvement in heat resistance and the like. The present invention has been completed.

Japanese Patent Laid-Open No. 04-208279 Japanese Patent Laid-Open No. 08-053436 Japanese Patent Laid-Open No. 04-029986 JP 05-214101 A

  Accordingly, the present invention provides novel bis-trimellitic anhydride esters that can be suitably used as curing agents or raw materials for epoxy resins, urethane resins or polyesterimide resins having improved heat resistance and mechanical strength. And a novel polyesterimide precursor obtained from it and a diamine.

In the present invention, as a trimellitic anhydride ester compound as a raw material of a heat-resistant polyesterimide resin, three methyl groups are substituted at specific positions of the cyclohexane ring of the central skeleton, which is a novel ester compound, of the following general formula (1) Bis-trimellitic anhydride ester having 1,1-bis (4-oxyphenyl) 3,3,5-trimethylcyclohexane as a central skeleton, and polyesterimide precursor of the following general formula (2) obtained from the compound and diamine Is to provide.

The bis trimellitic anhydride esters of the present invention have a structure in which three methyl groups are substituted at a specific position of the cyclohexane ring of the central skeleton, and such bis trimellitic anhydride esters are conventionally known. Not. Furthermore, it has been found that it has a melting point and glass transition temperature that are specifically higher than expected, while maintaining solubility in organic solvents as compared to the above-mentioned bis-trimellitic anhydride esters of the prior literature. The bis trimellitic anhydride esters according to the present invention are useful as curing agents such as epoxy resins and polyurethane resins which are industrially easy to handle and have improved heat resistance, and as polyimide resin raw materials. Further, a polyesterimide resin excellent in heat resistance and mechanical strength can be obtained from a polyesterimide precursor obtained from such bistrimellitic anhydride esters and diamines.
In addition, excellent properties with respect to water absorption, optical properties, and electrical properties can be expected.

（式中、Ｒ_１、Ｒ_２は各々独立して水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシル基、又はフェニル基を示す。）
また、本発明による今ひとつの新規な前駆体化合物は、上記のビス無水トリメリット酸エステル類とジアミンから得られるポリエステルイミド前駆体である。 The novel ester compounds according to the present invention are bis trimellitic anhydride esters represented by the following general formula (1).

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or a phenyl group.)
Another novel precursor compound according to the present invention is a polyesterimide precursor obtained from the above bistrimellitic anhydride esters and diamines.

In the bistrimellitic anhydride esters represented by the general formula (1), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atom. 8 represents an alkoxyl group or a phenyl group.
In R ₁ and R ₂ , the alkyl group having 1 to 8 carbon atoms is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 7 carbon atoms. It is. Specific examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group, and a cyclopentyl group.
The alkoxyl group having 1 to 8 carbon atoms is preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms or a cycloalkoxyl group having 5 to 7 carbon atoms. Specific examples of the alkoxyl group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, a cyclohexyloxy group, and a cyclopentyloxy group. In addition, 1 to 3 alkyl groups may be substituted on the phenyl group.
In the formula, R ₁ and R ₂ are preferably R ₁ and R ₂ when R ₁ and R ₂ are both hydrogen atoms, or when one is a hydrogen atom and the other is an alkyl group.

Therefore, as the bis trimellitic anhydride esters represented by the general formula (1), specifically, for example,
1,1-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane,

Furthermore, 1,1-bis {3-methyl-4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane,
1,1-bis {3,5-dimethyl-4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy} phenyl-3,3,5-trimethylcyclohexane,
1,1-bis {3-ethyl-4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane,
1,1-bis {3-cyclohexyl-4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane,
1,1-bis {3-methoxy-4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane,
1,1-bis {3-phenyl-4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane,
Etc.

  The production method of the bis trimellitic anhydride ester represented by the general formula (1) of the present invention is not particularly limited. For example, as described in JP-A-8-53436, bisphenol Or trimellitic anhydride halide in the presence of an amine, or a bisphenol lower alkanoic acid ester and trimellitic anhydride ester in the presence of a phase transfer catalyst as described in JP-A-2006-206486 It can be manufactured by a method similar to the replacement method. For example, a method for reacting bisphenol and trimellitic anhydride in the presence of an amine will be specifically described. As exemplified in the following reaction formula (1), the central skeleton of the bistrimellitic anhydride esters of the present invention is used. 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexanes represented by the following general formula (3) and trimellitic anhydride represented by the following general formula (4) Bis trimellitic anhydrides represented by the general formula (1) of the present invention can be obtained by reacting a halide in the presence of a tertiary amine in the absence of a solvent or in an organic solvent.

（一般式（３）中Ｒ_１、Ｒ_２は一般式（１）のそれと同じである。また、一般式（４）中Ｘはハロゲン原子を表す。）

(In general formula (3), R ₁ and R ₂ are the same as those in general formula (1). In general formula (4), X represents a halogen atom.)

Specific examples of the raw material bisphenol 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane represented by the general formula (3) include, for example,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
Etc.

In addition, as another raw material trimellitic anhydride halide represented by the general formula (4), specifically, for example, trimellitic anhydride chloride, trimellitic anhydride bromide, trimellitic anhydride iodide, etc. Can be mentioned.
In the reaction of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and trimellitic anhydride, trimellitic anhydride is 1,1-bis (4-hydroxyphenyl)- Usually, about 1.5 mol times or more of 3,3,5-trimethylcyclohexane is used, preferably in the range of 1.8 to 3.0 mol times, particularly preferably 2.0 to 2.5 mol. Used in the double range. In the reaction, trimellitic anhydride halides and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are reacted in an organic solvent in the presence of a tertiary amine.

Examples of the tertiary amines include pyridine, N, N-dimethylaniline, N-methyldiphenylamine, triethylamine, tributylamine, quinoline, acridine, pyrazine, imidazopyridine and the like. In particular, pyridine is preferably used. The amount of these tertiary amines used is required to be an equimolar amount or more with respect to the raw trimellitic acid halide, and is preferably used in the range of 1 to 1.5 times mol.
The organic solvent at the time of reaction may be omitted if there is no problem in operation by using many tertiary amines, but it is preferable to use an organic solvent. The organic solvent is not limited as long as it is a reaction raw material solvent and does not inhibit the reaction, but preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, 3, 3 , 5-trimethylcyclohexanone, methylpentyl ketone, 2-octanone, 2-tridecanone and other ketones, pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclopentane, cyclohexane, cycloheptane and other aliphatic hydrocarbons , Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and pseudocumene, ethers such as ether, diethyl ether and tetrahydrofuran, and carboxylic acids such as acetic acid. Of these, ketones such as acetone and methyl isobutyl ketone are preferred, and such solvents may be used alone or in admixture of two or more.

Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, Usually, 1-100 weight times with respect to raw material bisphenol, Preferably it is 2-30 weight times, More preferably, it is used in 5-15 weight times.
In the reaction, the method and sequence of charging the raw trimellitic anhydride halides, 1,1-bis (4-hydroxyphenyl) 3,3,5-trimethylcyclohexane, amines and reaction solvent into the reaction vessel Although there is no particular limitation, generally, trimellitic acid halide is dissolved in a solvent, charged into a reaction vessel, and then added to 1,1-bis (4-hydroxyphenyl) -3. , 3,5-trimethylcyclohexane in amines is dropped to react, or trimellitic acid halide is dissolved in a solvent and charged in a reaction vessel, and then amines are dropped into this. First, after forming an amine salt of trimellitic acid halide, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylsilane The Rohekisan acids dropwise a solution dissolved in a solvent, a method of reacting are preferred.
The reaction temperature is usually in the range of −10 to 100 ° C., preferably in the range of −10 to 30 ° C., and more preferably in the range of 0 to 10 ° C.

（一般式（５）中、Ｒ_１、Ｒ_２は一般式（１）のそれと同じである。） After completion of the reaction, a known purification method can be used to obtain the target product from the reaction product mixture. For example, an acid aqueous solution such as hydrochloric acid and water are added to the obtained reaction product mixture and washed with water. The aqueous layer containing the amine salt is removed. If necessary for separating and removing the aqueous layer, a water-separable solvent such as methyl isobutyl ketone, toluene or ether is added and dissolved, and then the aqueous layer is separated and the oil layer is washed with water. The resulting oil layer is subjected to a ring-closing reaction of tetracarboxylic acid that has been opened by adding acetic anhydride to form crystals by crystallization. If necessary such as low crystal purity, crystallization or precipitation may be performed once to several times. The obtained crystals are separated by filtration and dried to obtain the bis trimellitic anhydride esters of the present invention as high purity crystalline powder. Examples of crystallization solvents include aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisopropyl ketone, aromatic hydrocarbons such as toluene, xylene, mesitylene, and benzene, and saturated hydrocarbons such as pentane, hexane, and cyclohexane. can give.
As described above, when it is brought into contact with water by washing operation or the like, the target bistrimellitic anhydride ester reacts with water, and all or a part thereof becomes a tetracarboxylic acid of the following general formula (5). The target bistrimellitic anhydride ester can be obtained by a known method such as reacting a tetracarboxylic acid produced as exemplified by the following reaction formula (2) with a saturated aliphatic carboxylic acid anhydride. .

(In general formula (5), R ₁ and R ₂ are the same as those in general formula (1).)

（式中、Ｒ_１、Ｒ_２は各々独立して水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシル基、又はフェニル基を示し、Ａは２価の芳香族基及び／又は脂肪族基を示す。） Further, another novel precursor compound according to the present invention, a polyesterimide precursor (hereinafter, also referred to as polyamic acid) obtained from a bistrimellitic anhydride ester represented by the general formula (1) and a diamine, It is represented by the following general formula (2).

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or a phenyl group, and A represents a divalent aromatic group. A group and / or an aliphatic group.)

In the general formula (2), in the formula, R ₁ and R ₂ are the same as those in the general formula (1).
A represents a divalent aromatic group and / or an aliphatic group. A which is a divalent aromatic group and / or an aliphatic group is a divalent group in the diamine of the following general formula (6) in the following reaction formula (3) showing the production scheme for obtaining the polyesterimide precursor of the present invention. Same as A.

  In the above reaction formula (3), the diamine represented by the general formula (6) containing a divalent aromatic group and / or an aliphatic group represented by A may be a tetracarboxylic dianhydride according to the present invention. If it is an aromatic and / or aliphatic diamine which can react with trimellitic anhydride ester and can obtain a polyesterimide precursor, there will be no restriction | limiting in particular.

  Specifically, for example, aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4′-diaminodiphenylmethane, 4,4′-methylenebis (2-methylaniline), 4,4′-methylenebis (2-ethylaniline), 4,4′-methylenebis (2,6-dimethylaniline), 4 , 4′-methylenebis (2,6-diethylaniline), 1,3-bis {1- (4-aminophenyl) isopropyl} benzene, 1,4-bis {1- (4-aminophenyl) isopropyl} benzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether 2,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzanilide 4-aminophenyl-4′-aminobenzoate, 4-amino-2-methylphenyl-4′-aminobenzoate, bis (4-aminophenyl) terephthalate, bis (4-amino-2-methylphenyl) terephthalate, benzidine 3,3′-dihydroxybenzidine, 3,3′-dimethoxybenzidine, o-tolidine, m-tolidine, 2,2′-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3 -Bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) Sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, p-terphenylenediamine, bis (4-aminophenyl) terephthalate, bis (4-amino-2-methylphenyl) terephthalate and the like.

  Specific examples of the aliphatic diamine include 4,4′-methylenebis (cyclohexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4- Cyclohexane bis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (Aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-he Sa diamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylenediamine, and the like. Such aromatic or aliphatic diamines may be used alone or in combination of any two or more.

As the polyesterimide precursor having a repeating unit represented by the general formula (2) of the present invention, a known method can be used for its production method. Specifically, for example, the diamine represented by the general formula (6) is dissolved in a polymerization solvent, and the bistrimellitic anhydride esters of the present invention (usually in powder form) are gradually added thereto. For example, the reaction is performed with stirring using a mechanical stirrer or the like. The reaction temperature and reaction time depend on the raw materials and solvents used, but are usually in the range of temperature 0-100 ° C, preferably 20-60 ° C, 0.5-100 hours, preferably 1-24 hours. React. Moreover, in order to accelerate | stimulate reaction, the aspect using an anhydrous solvent or making it react in nitrogen atmosphere is also suitable.
In the reaction, the monomer concentration in the resulting reaction mixture is usually 5 to 50% by weight, particularly preferably 10 to 30% by weight. By carrying out polymerization in this monomer concentration range, a polyimide precursor having a uniform and high degree of polymerization can be obtained.

The intrinsic viscosity of the polyesterimide precursor represented by the general formula (2) of the present invention thus obtained varies depending on the bistrimellitic anhydride esters and diamines used, but is usually 0.1 to 20.0 dL. / G, preferably 0.5 to 5.0 dL / g.
The polyesterimide precursor represented by the general formula (2) of the present invention may be used as a varnish containing a solvent, or may be used in other forms such as a solid depending on the intended use.
In the reaction, as the tetracarboxylic dianhydride, other tetracarboxylic dianhydrides may be used in combination with the bistrimellitic anhydride esters of the present invention.

  Specific examples of such tetracarboxylic dianhydride include, for example, aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. Anhydride, hydroquinone-bis (trimellitic anhydride), methylhydroquinone-bis (trimellitic anhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4 '-Benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propa Dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, and the like 2,3,6,7-naphthalene tetracarboxylic dianhydride.

  Further, as the aliphatic tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (dioxotetrahydrofuryl-3) -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4 , 5-tetracarboxylic dianhydride, bicyclo-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 , 4-cyclopentanetetracarboxylic dianhydride, etc. Further, two or more of these other tetracarboxylic dianhydrides may be used in combination.

In the reaction, a polymerization solvent may or may not be used, but is preferably used for operation, and the polymerization solvent has an appropriate solubility with respect to the raw material bis trimellitic anhydride esters and diamine, There is no particular limitation as long as it does not inhibit the condensation reaction. Specifically, for example, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1-methyl-2-pyrrolidone, etc. , Γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, cyclic ester solvents such as α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, m-cresol, Phenols such as p-cresol, 3-chlorophenol, 4-chlorophenol Examples thereof include a solvent, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like.
Of these, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, dimethylformamide, 1-methyl-2-pyrrolidone, etc. A polar solvent is preferably used.

In addition, other common organic solvents can be used in combination with such a solvent as a mixed solvent. Specific examples of such organic solvents include phenol, 0-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, and dimethoxyethane. , Diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, toluene, chlorobenzene, terpene, mineral spirit, petroleum naphtha solvents and the like.
Moreover, the terminal of a polyamic acid can also be sealed. In the case of sealing with an end-capping agent, examples of the end-capping agent include phthalic acid chloride and substituted products thereof, and examples of the amine component include aniline and substituted products thereof.

（式中、Ｒ_１、Ｒ_２及びＡは一般式（２）のそれと同じである。） The polyamic acid represented by the general formula (2) of the present invention is an iteratively represented by the following general formula (7) by imidizing the polyamic acid thermally or using a dehydrating cyclization reagent or the like by a known method. It can be set as the polyesterimide resin which has a unit.

(In the formula, R ₁ , R ₂ and A are the same as those in the general formula (2).)

（式中、エステル基の結合位置は、アミド結合に対してメタ位又はパラ位である） Specific examples of the polyesterimide resin having a repeating unit represented by the general formula (7) include, for example, R ₁ and R ₂ are hydrogen atoms, and amine is 1,3-bis {1- (4 The case of -aminophenyl) isopropyl} benzene is shown by the following reaction formula (4).

(In the formula, the bonding position of the ester group is meta position or para position with respect to the amide bond)

Example 1
Synthesis of 1,1-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane;
A 1 L four-necked flask equipped with a reflux condenser and a dropping funnel was charged with 60.5 g (0.297 mol) of trimellitic anhydride chloride, 233 g of methyl isobutyl ketone, and 97 g of acetone, and dissolved while cooling to 0 to 5 ° C. It was. Separately, 38.8 g (0.125 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 29.7 g (0.375 mol) of pyridine and 38.8 g of methyl isobutyl ketone were obtained. After mixing and dissolving at room temperature, this solution was added dropwise to the four-necked flask with a dropping funnel over 2.5 hours while maintaining the temperature at 0 to 5 ° C., and the reaction was carried out with stirring. After completion of the dropwise addition, the mixture was further reacted with stirring at a temperature of 0 to 5 ° C. for 1 hour, then the temperature was raised to 70 ° C. and the mixture was further reacted with stirring for 5 hours. After completion of the reaction, aqueous hydrochloric acid and water were added and stirred, and then the aqueous layer was separated. Water was added to the obtained oil layer and stirred, and then the water washing operation for separating the aqueous layer was repeated 4 times to remove the produced pyridine hydrochloride. Thereafter, 48.5 g (0.475 mol) of acetic anhydride was added to the oil layer containing the tetracarboxylic acid whose target product was ring-opened at the time of washing with water, and the ring was closed at a temperature of 85 to 90 ° C. over 1.5 hours. The crystals precipitated upon cooling were filtered to obtain white crystals having a purity of 97.8% (according to gel permeation chromatography analysis). The yield based on the raw material bisphenol was 74 mol%.

Melting point: 211 ° C. (by differential scanning calorimetry)
1H-NMR analysis (400 MHz, solvent: CD ₃ Cl)

（式中、エステル基の結合位置は、アミド結合に対してメタ位又はパラ位を表す） (Example 2)
Synthesis of polyimide precursor (polyamic acid);
1,1-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3,3,5-trimethylcyclohexane obtained in Example 1 was used as an organic solvent. 1,1-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} -3, having a purity of 99.0 mol%, 3,5-Trimethylcyclohexane powder was obtained and used as a polyimide precursor raw material.
Next, 6.89 g (0.020 mol) of 1,3-bis {1- (4-aminophenyl) isopropyl} benzene and 120.3 g of N-methylpyrrolidone were charged into a nitrogen-substituted 300 ml four-necked flask at a temperature of It was dissolved at 30 ° C. Thereafter, the powdery 1,1-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl}-was maintained while maintaining the temperature at 30 ° C. in a nitrogen atmosphere. 13.3 g (0.020 mol) of 3,3,5-trimethylcyclohexane was added over 30 minutes. After completion of the addition, the reaction was performed with stirring at a temperature of 30 ° C. for 18 hours. After completion of the reaction, the obtained reaction solution was analyzed by GPC (gel permeation chromatography), and the polymer molecular weight was 22410 (polystyrene equivalent value). The viscosity of the reaction solution was measured to be 8.0 poise.
Moreover, it confirmed that the obtained polymer was the polyimide precursor of the target object represented by following Chemical formula from GPC analysis.
Conversion

(In the formula, the bonding position of the ester group represents the meta position or the para position with respect to the amide bond)

(Comparative Example 1)
In Example 1, instead of (1) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, (2) 1,1-bis (4-hydroxyphenyl)- Bis-trimellitic anhydride bisphenol esters (2) and (3) were synthesized in the same manner as in Example 1 except that cyclohexane and (3) 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) were used. The compound physical properties were compared in Table 2 below.
Thus, the bis trimellitic anhydride ester (1) according to the present invention exhibits a high melting point and a glass transition point, and also has good solubility in a solvent.

溶解度測定方法；
各化合物１０．０ｇに溶媒１０．０ｇを加えて、撹拌下に９０℃（テトラヒドロフランの場合は３０℃）に昇温し、同温度で２分間溶解させた後、結晶が完全に溶解しているか確認した。結晶が溶け残っていたので、溶媒１０．０ｇを追加して同様の操作で溶解させた。その後、結晶が完全に溶解するまで、溶媒を追加して同様の操作を行った。化合物が完全に溶解した時点の全溶媒量より溶解度を算出した。
ガラス転移温度測定方法：
示差走査熱量計において各化合物の結晶の融点より２０℃高い温度まで昇温して、融解させた後、冷却し、更に、その後、加熱して、ガラス転移点を測定した。この際の測定条件は、測定開始温度４０℃、測定終了温度融点＋２０℃、加熱速度１０．０℃／分とした。

Solubility measurement method;
After 10.0 g of solvent is added to 10.0 g of each compound, the temperature is raised to 90 ° C. (30 ° C. in the case of tetrahydrofuran) with stirring, and after dissolving for 2 minutes at the same temperature, is the crystal completely dissolved? confirmed. Since crystals remained undissolved, 10.0 g of solvent was added and dissolved by the same operation. Thereafter, the same operation was performed by adding a solvent until the crystals were completely dissolved. Solubility was calculated from the total amount of solvent when the compound was completely dissolved.
Glass transition temperature measurement method:
In a differential scanning calorimeter, the temperature was raised to a temperature 20 ° C. higher than the melting point of the crystals of each compound, and after melting, the mixture was cooled and then heated to measure the glass transition point. The measurement conditions at this time were a measurement start temperature of 40 ° C., a measurement end temperature melting point of + 20 ° C., and a heating rate of 10.0 ° C./min.

Claims (2)

Bis-trimellitic anhydride esters represented by the following general formula (1).

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or a phenyl group.) The polyesterimide precursor which has a repeating unit represented by following General formula (2).

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or a phenyl group, and A represents a divalent aromatic group. Group and / or aliphatic group, and the bonding position of the ester group represents the meta position or the para position with respect to the amide bond.)